Process for the polymerization of aliphatic aldehydes



May 4 1943- B. THoMPsoN PROCESS FOR THE'POLYMERIZATIONv OF ALIPHATIC ALDEHYDES Filed July 22, 1957 Er mgm ESSE A ENE mmm NN uz: @t

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.Benjaminl Thngzz/n A0113 A NN . rial interruption of the process. i, ject is to provide a processfcr the production of ,paraldehyde from acetaldehyde wherein the Patented May 4, 1943 PROCESS FOR THE POQYMERI'ZATION OF ALIPHATIC ALDEHYDES 4Benjamin Thompson, Kingsport, Tenn., assgnor to Eastman Kodak Company, Rochester, N. Y., a corporation of New Jersey Application July 22, 1937, Serial No. 155,064

11v Claims. (Cl. 260-340) This invention relates to processes for the poly-v' merization of aliphatic aldehydes, and more particularly to a continuous process for polymerizing `acetaldehyde toparaldehyde.

-The polymerized products of aliphatic aldehydes have a largernumber of commercial uses, consequently, a number of methods for the preparation of such materials have been developed. However, many of these processes are only susceptible to being carried out on a small intermittent scale, inasmuch as they are primarily directed to batch operation.

I have found a method for the polymerization of aliphatic aldehydes which may be continuouslyoperate'd with the production of high yields of the desired product.

One object of` my invention is to provide a process for the polymerization of aliphatic aldehyde'swhich is continuous. Still another object is-to provide a catalytic process for the polymerizationof aliphatic aldehydes wherein the catalystmay be replaced and introduced without mate- A further obyields are improved.

Still another object is to provide a procedure for refining and otherwise improving crude polymerized products. Still another object is to provide a method of distilling mixtures containing paraldehyde in order to recover relatively pure `paraldehyde therefrom. y

column which contains the reacting solution of A aliphatic aldehyde, polymerized aldehyde and g Another object is to provide apparatus for carrying vout a continuous process for the -polymerization of aliphatic aldehydes. A still further object is to provide an apparatus wherein the catafurther object is to provide an apparatus for the preparation of paraldehyde wherein the formed paraldehyde may be subjected to cooling treatments. j

These objects are accomplished by my novel process wherein aliphatic aldehydes are polymerized andthe resultant products subjected to treatments which increase the yield and improve the quality of the products of polymerization.

`My novel process may be better understood by reference to the accompanying drawing which forms a part of'the present invention:

The attached gure is aHsemi-diagrammatic side elevation showing my apparatus set up for continuously polymerizving an aliphatic aldehyde. Certain parts have been shown broken away or on section for clarity. y

. In the figure 2 designates a reaction vessel or catalyst. The temperature in this reaction vessel or column is controlled by means of jackets 3 and 4. In place of these temperature controlling jackets, cooling coils or cooling plates may be introduced into the column, or other equivalent means employed. 'I'he column 2 terminates in a cone-shaped or sump construction 6. This construction is connected through valved conduit 1, pump 8 and conduit 9 to a catalyst reservoir Il.

Catalyst reservoir II is connected to the upper portion of the reaction tower 2 by means of 'valved conduit I2.

The upper portion of the reaction twer is also provided with a vent means, designated I3. Thisv lmeans may comprise a conduit I4 enclosedby a condenser I6. Extending into the reaction tower 2 at some intermediate point I1 are inlet con- A duits IIB or I9. These conduits terminate in a diii'user or spray head 2|.

Conduit 22 connects the lower part of the reaction tower with cooling chamber 23. 4'I'his cooling chambermay be of various constructions andwill comprise a tank 24 having associated therewith temperature controlling means 26. As indicated with respect to tower 2, the temperature controlling means may comprise a jacket ,external of the tank, or cooling coilsl or equivalent means maybe inserted in the tank. The upper portion of the tank 24' is connected by means of conduit 21 to a mixing vessel 28.

This mixing'vessel may be of any usual construction, and contains anl agitator 29, charging openlyst maybe removed or supplemented. A still i i ing 3| and valved draw-oli 32. Mixing vessel'28 Ais connected by means o conduit 33 to afeed heater or vaporizer 34,-wl'iich, in turn, is connected to the intermediate section of a.` distillation column 36. These parts 34, 36 and associated vparts, are similar to the distillation columns shown in U. S. Patent 1,908,239 and Gordon Patheater 4I which contains heating means 42. In

, device.

place of this-base heaterv construction described it is possible to employ a calandria. type heating with a. dephlegmator 41 for furnishing redux. The conduit 48 connects the ,upper portion-of A sediment draw-oli isr provided at 43.v

Y or the like. The refrigerated reflux condenser attachedn to .conduit Il, is provided for preventthe column through condenser 49 to receiver 5I.

The vent conduit 62 leads through another condenser 5,3 back to aldehyde feed or storage.

The functioning of these various pieces of apparatus will be more apparent from the following example, which is set forth merely to illustrate a, preferred form of my invention.

Assuming that my process is in operation for the manufacture of paraldehyde from acetaldehyde, the reaction tower 2 contains a solution of various inorganic acids, may be employed, or. if desired,- hydrochloric acid gas may be injected into the reaction mixture. The catalyst may, if4 desired, be in a solvent such as acetone, organic acids'and ethers. I find that a 50%-80% solution of sulfuric acid (without an organic solvent) is quite satisfactory.

In: the instances where a solvent is employed, similar quantities of catalyst also function satisfactorily.' l

The sulfuric acid is slowly fed into the reaction vessel Afrom the catalyst reservoir Il. Itv

mixes with and dissolves in the reaction mixture upto its solubility'limit. Any excess catalyst falls to the bottom of the reaction tower as at 6, and is withdrawn through conduit 1, from which it may be pumped-through conduit S back to the catalyst reservoir. Preferably, I employ a catalyst concentration below its solubility limit, hence the aforementioned feature may be dispensed with. However, it may be useful in instances where excess catalyst has been 'added In the catalyst reservoir additional sulfuric acid may be supplied to make up for that consumed or lost in the reaction.

Acetaldehyde is fed into the reaction liquid contained in tower 2 at some intermediate point. Preferably, the acetaldehyde is injected below the surface of the reaction mixture. I nd that highly desirable results are obtained by injecting an oxygen-free acetaldehyde into a reaction mixture maintained approximately between and' 35 C., although higher or lower temperatures may be employed, as 10 C. to 100 C., for example.

By feedingv thel aldehyde through conduit I8 into` and below the surface of the reaction mixture, it absorbs part of the heat from the reaction mixture and thereby becomes partially or entirely vaporized on entering the reaction mixture through distributing device 2|. The risingof thevapors through the reaction mixture provides mixing and solution.`- While such procedure In accordance with my preferred procedure,

the reaction product containing paraldehyde is withdrawn into cooling chamber 24. In this chamber the velocity of flow will be low enough to permit any suspended catalyst to settle. In

addition, the reaction mixture may be cooled by means of circulating acooling medium in the jacket 26. I have found that cooling and main-v taining the reaction mixture at a temperature from about 10 to 25f C. causes a, favorable shift in-the reaction equilibrium toward the formation of paraldehyde. Also, the solubility of catalyst in the reaction materials is reduced. That is, this treatment, which comprises subjectingthe reaction mixture to cooling in chamber 24. improves the yields of paraldehyde obtained. I find that holding the unneutralized crude paraldehyde mixture for several hours at approximately 10 to 25 (3.'before passing it to the refining treatment, to be described hereinafter, is highly desirable.

'Ihe crude reaction product containing paraldehyde overiiows through conduit 21 into mixing vessel 28. The continuous introductionof acetaldehyde into either feed lines I8 or i9, .or both will cause an equivalent amount of reaction rnaterial to be displaced from reaction tower 2. In mixing vessel 28 the crude paraldehyde is preferably subjected to the following novel treatj ment. The crudewould be agitated with alkali carbonate, in slight excess over the acid present, for'about ten minutes to about two hours and the treatment would be followed by agitating with a small per cent (0.002% to .05%) of ammonia for a short period, of, for example, 5 to Y 15 minutes. Note is made of the fact that the crude preferably would be vaporized in the presence of excess alkali carbonate. It is then vaporlzed directly from the neutralized salts and I excess carbonate. ,K'Ihe steps may be further ilcomprises desirable technique, I find that the acetaldehyde may alsobe fed to distributing de- -vice 2|, through conduit I9, and, if necessary, mechanical agitation may be supplied in the reaction tower.

As already indicated, I prefer to employ an oxygen-free acetaldehyde and to carry out the reaction intheabsence-of an oxidizing atmosphere. This may be .obtained by evacuation or the displacement of any air or oxygen contained such as nitrogenv in the chamber bydnert gas. s

ing the loss of acetaldehyde vapors from the system. It isjalso possible at this point to evacnate anyair vfrom the system or to inject an` lustrated by the following example:

I have found that paraldehyde (produced from acetaldehyde using a sulphuric acid catalyst) tends to go back to acetaldehyde on distillation at atmospheric pressure even` though an excess of NazCOs is used in neutralizing the acid catalyst and acetic acid formed. I havefound that this reversal may be prevented by the addition of a very small quantity of ammonium hydroxide or gaseous ammonia as desired. For example, ina 2,500 1b. batch of crude paraldehyde containing .0'1 to .3% HiSO4, 5-10% unconverted aldehyde,

and 90-95'% paraldehyde, enough NaaCOt4 is added ,to be 25 to 50% in` excess of the I-I/:SO4 content and agitated 30 minutes then 1 lb. of ammonium hydroxide (28% NH3) is added and the agitation continued for a few minutes before distillation. The temperature is kept 1020 C.

-until the catalyst has been neutralized and NHiOI-I, added. The amount of acetaldehyde distilled off corresponds to the analysis before distillation and the paraldehyde contained less than 1% acetaldehyde. Complete neutralization canY be done wtih' ammonia'y but4 this is not necessary.`

various alkali bonates or hydroxides, such 'as calcium or sodium carbonate. calcium hydmxide or' the like, in ,ai drynr anhydrous condition.

may be employed. Any sludge and the like formed may be removed from mixer 28 through `is prolonged, or if reduced pressure is used. The Vammonia treatment may not be employed if other acids than H2504 are used as catalyst. H2504 as catalyst, however, has much advantage over other acids in the rapid and continuous productionbf crude.

The improved crude paraldehyde then overows through conduit 33 into the feed evaporator 34. This mixture in 34, which contains paraldehyde, water formed by neutralization and various other sources, and unreacted acetaldehyde is vaporizedand passes through conduit 39 into distillation column 36, any residue being withdrawn at 38.

The paraldehyde mixture in 36 is rectified and water, paraldehyde and acetaldehyde pass through conduit .48, condenser 49; the paraldehyde and water being collected at I. A part of the vapors passing to cond-uit 48 are condensed at 41 and returned as reflux. In lieu thereof, however, a part of the condensate collected in receiver 5| may be returned to the head of the column at 41 for reflux. The aldehyde vapors escape from receiver 5| through conduit 52 and may be liqueed by means of condenser 53 from which they are returned to storage feed, or other use. The paraldehyde withdrawn from 5I may also be re-employed in the process. With further regard to this distillation, condenser-49 i distilled, it is' highly desirable thatall traces of may be run hot so that the acetaldehyde would be ashed 01T to the next condenser. This would permit the paraldehyde and water to separate into two phasea in which case receiver 5I would also be constructed as a decanter from which the top paraldehyde layer would be returned as reflux and water layer only beingwithdrawn at the bottom.

At the base of column 36 the rened paraldehyde may be removed as a liquid, or it may be vaporized through 44 and condensed at 46. Either atmospheric or vacuum distillation may be employed. The use of an inert atmosphere or the absence of oxidizing conditions is pre-v ferred in the distilling step, as in other parts of the process. The maintenance of such conditions in my process increases the velocity off polymerization, and by its use, a saving .in size of equipment and time of reaction obtained.

Although I have described a process carried out at atmospheric pressure, I also propose to polymerize acetaldehyde to paraldehyde under moderate pressures, Athat is -up to 100 pounds gauge. This may easily be accomplished 'continuously in the apparatusand processs described. The useof pressure would be confined to the reaction vessel and its reux condenser.'

'I'he advantage in the use of pressure lies in er1--l abling the major portion of the reaction' to be carried out at a higher temperature. The higher temperature in turn permitting the use of warmer and less expensive cooling medium thus reducing refrigerationl costs. 4-

For example by using 30, pounds pressure the boiling point of acetaldehyde is raised to approximately 51 C. This would permit a reaction temperature in the range of 70 C. This would permit water to be used to carry away the bulk of heat of reaction liberated in the top section of the reaction vessel and in its condenser.

For example, I have used 18.C. brine. The capacity `of a refrigerating machine producing brine at 18 C. is less than half of its rating in tons of refrigeration in producing brine at 0 C. Yet the use of but 15 pounds pressure in the reaction chamber permits the use of 0 C. brine and still permits the same temperature difference in the reaction vessel.

Tlius large-savings can be effected bythe use of only moderate'pressures in the reaction vessel.

From a consideration of the above examples,V

it is apparent that I have provided novel procedure whereby an aliphatic aldehyde may be converted to polymers thereof. My process' and apparatus possess a number of advantages. For example, the reaction of air-aldehyde to form an acid polymerization product, such as paraldehyde, as well as the reaction withan alkaline catalyst to form an'aldol are strongly exothermic, and if the heat is not carriedaway rapidly, a tar formation may result. Hence, in carrying out the reaction, if a batch system is used involving a large body of aldehyde', it is very diilcult to carry away the large vamount of heat. However, my process and apparatus have the advantage over batch-wise processes in that only a small volume of highly reactive aldehyde is present at any one time. This is'desirable' in that it removes the possibility of a largefbatch of aldehyde reacting more rapidly than the cooling means can control and thus becoming too violent.

The advantage of feeding the aldehyde below the surface and preferably somewhere near the center of the vessel can be seen more readily by considering the vessel to be in two sections. In the top section, from slightly below the diffuser 2|V to the surface, the bulk of the reaction occurs. The constant boilngof the incoming liquid and vapor of acetaldehyde provides rapid agitation, giving better heat transferin this top section in which most of the heat must be removed. The boiling also accomplishes even distribution to the very small amount of catalyst and prevents layers of unreacted aldehyde. from forming in the reaction chamber. In operation the temperature of the feed and this section of the reaction vessel are preferably controlled so that boiling of the aldehyde is smooth and merely sucient to'cause good agitation. Boiling is`moderate enough' so that only a small part of the feed must be condensed in the reflux condenser I6.

In addition to mixing caused by boiling as the liquid in the top section becomes strongin product the paraldehycte falls to thelower section due to its higher gravity. Thisalso is of aid in causing rapid distribution- 'of catalyst and pre- .vantage cf the diil'erence in gravity of the product over the aldehyde and the more reacted por-l tions of liquid fall to the base and are withdrawn first. This veffect is denite and visible inl glassas they are particularly 4 .saturated aliphatic .tion in which the bulk of reaction may be carried out in a small vessel having a high cooling surface to volume ratio and having only a small volume of highly reactive material involved at any one time in connection with a larger vessel having a largevolume to surface ratio in which the reaction is carried to equilibrium, thus permitting cooling surfaces to be used at high efflciency at all times.

Although I have described my process and apparatus particularly with respect to the polymerization of acetaldehyde to paraldehyde, inasmuch suitable for this reaction,

my invention has wider application. For example, propionaldehyde and various other higher aldehydes may be polymerized in my apparatus. By altering temperature and other conditions of operation, acetaldehyde may be continuously converted into metaldehyde. By the addition of alkalil catalyst at Il, my apparatus may be employed for the production of alkali condensation products of aldehydes. That is, aldol may -be continuously manufactured by adding a sodium hydroxide or. other alkali solution at il. The temperature of the apparatus would be maintained at between about 5 25 formed would be removed to the neutralizer 29 where in this instance acid, such as acetic acid, would be added. Therefore, my invention is not to be restricted except insofar as necessitated by the prior art and the spirit of the appended claims.

What I claim is:

1. A process for the-production of pure paraldehyde which comprises subjecting a mixture containing paraldehyde, acetaldehyde and an inorganic acid component to'treatment with an alkali, vaporizing the treated reaction materials and conducting the vapors to an intermediate point of a rectification treatment, withdrawing C. The aldol l paraldehyde, water and aldehyde as head products in the rectification treatment, and' withdrawing puried paraldehyde from a lower point in the distillation treatment.

2. In a process for the production of a rela- `tively pure aldehyde reaction product, the steps which comprise subjecting a mixture containing said`reaction product, unreacted aldehyde, and neutralizing component, to a vaporization treatment wherein the volatilized aldehyde andreaction product are vaporized away from the solid residue to `an. intermediate point of a rectification treatment, applying the rectification treatment to said volatilized components, and withdrawing aldehyde and water as rectification treatment, and withdrawing the puriedaldehyde reaction product from a lower point in this rectification.

3. I n a continuous process for producing reaction products comprising homologues thereof by polymerization of a lower aldehyde having at least two carbon atoms in its molecule, the steps which paraldehyde and` head products from the ture comprising said aldehyde, ,uct being produced and an acidic polymerization quiescent zone.

comprise injecting said lower; aliphatic aldehyde below the `siu'face of an elongated reactimiy mixthe reactionprodcatalyst, so that the -entry of the lower aliphatic aldehyde below the ksurface causes substantial agitation and mixing, permitting theA reaction product to flow downwardly and below the point of said aldehyde introduction to a quiescent zone and substantially continuously removing the product from said quiescent zone. Y

4. In a continuous process for producing the reaction products comprised of paraldehyde and homologues thereof by polymerization of a lower saturated aliphatic aldehyde havingat least two carbon atoms in its molecule, the steps which comprise introducing said lower aliphatic aldehyde below the surface of an elongated reaction mixture comprised of 'said aldehyde, the reaction product therefrom, and catalyst, so that the entry of the aldehyde below the surface causes agitation and mixing, conducting the introduction of aldehyde and polymerization thereof under a gauge pressure up to pounds per square inch, permitting the reaction product to ow downwardly and below the point of said aldehyde introduction to a quiescent zone and substantially continuously removing the product from said 5. In a continuous process for producing reaction products comprising paraldehyde and homologues thereof by polymerization of a lower saturated aliphatic aldehyde having at least two car- 'bon atoms in its molecule, the step which comprises introducing a substantially oxygen-free lower aliphatic aldehyde below the surface of an elongated reaction mixture comprising said aldehyde, the reaction product being produced and an acidic polymerization catalyst, so that the entry of the lower aliphatic aldehyde below the surface causes substantial agitation and mixing, permitting the reaction product to :dow downwardly and below the point of said aldehyde introduction to a quiescent zone and substantially continuously removing the product from said quiescent zone.

6. In a continuous process for producing reaction products comprising paraldehyde and homologues thereof by polymerization of a lower saturated aliphatic aldehyde having at least two carbon atoms in its molecule, the steps which comprise introducing a substantially acetic acid-free acetaldehyde below the surface of an elongated reaction mixture comprising said aldehyde, the reaction product beingV produced and an acidic polymerization catalyst, so that the entry of the lower aliphatic aldehyde below the surface causes substantial agitation and mixing, permitting the reaction product to ilow downwardly and below the point of said aldehyde introduction to a quiescent zone and substantially continuously removing the product from said quiescent zone.

7. In a continuous process for producing reaction products comprising paraldehyde and homologues thereof by polymerization of a lower saturatedaliphatic aldehyde having at least two carbon atoms in its molecule, the steps which comprise injecting said lower aliphatic aldehyde below the surface of an elongated reaction mixture comprising said aldehyde, the reaction product being produced and an acidic polymerization catalyst, so that the entry of the lower aliphatic aldehyde below the surface causes substantial agitation and mixing. Permitting the reaction product to flow downwardly and below the point of said aldehyde introduction to a quiescent zone, substantially continuously removing the reaction product from said quiescent zone and holding the withdrawn reaction product for a period in another reaction zone at a lower temperature than the temperature prevailing at the point of introduction of the aldehyde.

8. A processv for polymerizing acetaldehyde which comprises substantially continuously ine jecting acetaldehyde below the surface of an elongated reaction mixture under a gauge pressure between -#60 pounds,.said reaction mixture comprising an inorganic acid catalyst, the product of the reaction, and acetaldehyde, said in-g jecting of aldehyde causing agitation and mixing within the reaction mixture, maintaining the reaction mixture at a temperature between 5 C. and 80 C., withdrawing at least a part of the reaction product from the reaction mixture and holding the withdrawn product in a cooler for at least the major part of one hours time. 1

9. A process for producing pure paraldehyde which comprises substantially continuously contacting acetaldehyde with an elongated reaction mixture containing sulfuric acid under conditions drawing atleast a part of the paraldehyde formed.

by the reaction, conducting the withdrawn paraldehyde to a cooler, holding the paraldehyde therein for at least a fraction of an hour, then subjecting it to treatment which neutralizes any sulfuric acid contained therein, -and subjecting the neutralized paraldehyde mixture to a distil. lation treatment wherein paraldehyde, water and acetaldehyde are obtained as head purified paraldehyde as a tail product.

l0. .A process for treating acetaldehyde which comprises substantially continuously injecting acetaldehyde a substantial distance underneath the surface of and into the main body of an elongated reactlon mixture whereby agitation is obtained, maintaining the reaction mixture under pressure and at a temperature above 10 C., reflux-condensing vapors evolved from this reaction mixture, gravity-separating a product strong in paraldehyde, and collecting the product at a point substantially below the feed.

1l. A process for polymerizing a lower aliphatic g aldehyde which comprises substantially continuously injecting lower `aliphatic aldehyde below temperature between 5 C.' and 80" C., withdrawing at least part of the reaction product from the reaction mixture and holding the withdrawn` product in a cooler io at least the major part of one hour.

BENJAMIN THOMPSQN.

products and 

